THE  CATALYTIC  PREPARATION  OF  HYDROXYLAMINE 


BY 

VALENTINE  AUSTIN  JONES 
B.  S.  University  of  Illinois 
1921 

THESIS 

Submitted  in  Partial  Fulfillment  of  the 
Requirements  for  the  Degree  of 
MASTER  OF  SCIENCE 
IN  CHEMISTRY 

IN 

THE  GRADUATE  SCHOOL 

OF  THE 

UNIVERSITY  OF  ILLINOIS 


1922 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


January  19, 192J? 


I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 


SUPERVISION  BY- 


Valenti  ns  Austin  jLcnes 


ENTITLED The  Catalytic  Preparation  cf  K ydroxylarjjne 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 
THE  DEGREE  OF jjastery_of  Science 


Recommendation  concurred  in* 


Committee 

on 


Final  Examination* 


*Required  for  doctor’s  degree  but  not  for  master’s 


438978 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/catalyticpreparaOOjone 


Acknowledgment 

The  writer  wishes  to  express 
his  appreciation  and  sincere 
thanks  to  Doctor  J.H. Reedy 
for  his  assistance  in  the 
experimental  work, and  also 
for  his  aid  in  writing  this 


thesis 


Table  of  Contents 


I.  Introduction. 

II.  Historical. 

III.  Purpose  of  Research. 

IV.  Experimental. 

V.  Discussion. 

VI .  Summary . 

VII.  Bibliography. 


The  Catalytic  Preparation  of  Hydroxylamine. 


I . Introduction . 

The  question  of  procuring  a good  yield  of  Hydroxylamine 
by  a simple  and  inexpensive  method  has  been  the  subject  of  consi- 
derable investigation  by  chemists  for  many  years.  A few  methods 
have  been  suggested  and  used  for  its  preparation, but  in  all  the 
yields  are  not  good, and  the  methods  of  separation  from  by-products 
are  difficult  and  not  conducive  to  complete  separation.  Reduction 
of  nitrites , nitric  acid  and  nitric  oxide  to  Hydroxylamine  by  such 
reducing  agents  as  sulphurous  acid, chromous  chloride, hydrogen 
sulphide .hydrogen, etc. , have  been  attempted  with  but  indifferent 
success , mainly , because  of  the  fact  that  a good  method  of  separation 
was  lacking  or  that  the  reduction  did  not  stop  at  Hydroxylamine, 
but  continued  further  to  give  nitrous  oxide, nitrogen  or  ammonia. 

It  was  noticed  by  Victor  Meyer  and  others  that  often  some 
substance  used  as  a catalyser  or  by-products  of  the  reactions 
would  cause  the  immediate  decomposotion  of  any  Hydroxylamine  which 
might  be  formed.  The  urgent  need  of  a catalyser  which  could  be  used 
to  facilitate  the  reduction  of  nitric  oxide  to  Hydroxylamine  alone 
and  still  not  cause  the  decomposition  of  the  Hydroxylamine  formed, 
seeias  a paramount  necessity  if  we  expect  to  obtain  Hydroxylamine 
in  nearly  theoretical  amounts. 


' 


II*  Historical 


In  1834  Faraday ' published  an  article  wherein  he  described 
some  experiments  on  the  use  of  platinum  sponge  as  a catalyser. 

Among  the  reactions  he  experminted  with  was  the  reduction  of  nitric 
oxide  by  means  of  hydrogen  using  the  platinum  sponge  as  a catalyses 
He  passed  a mixture  of  hydrogen  and  nitric  oxide  slowly  over  pla- 
tinum sponge  at  room  temperature.  Reduction  of  the  nitric  oxide 
took  place  but  his  final  product  was  not  Hydroxylamine  as  he  ex- 

X 3 

pected  but  ammonia  and  water.  F.Kuhlmann  and  Jouve“also  working 
on  the  reduction  of  nitric  oxide  by  hydrogen  with  the  use  of  pla- 
tinum sponge  as  a catalyser  obtained  ammonia  and  water  as  the 
final  product, altho  Jouve  working  at  temperatures  not  exceeding 
115°C, claims  to  have  obtained  1-2 % of  Hydroxylamine. 

Cooke  working  with  a mixture  of  nitric  oxide  and  hydrogen 
and  using  platinum  sponge  as  a catalyser , states  that  he  obtained 
ammonia, Hydroxylamine  and  nitrous  oxide,  the  amounts  of  which  he 
does  not  mention  in  his  paper.  He  states  that  if  one  uses  nitric 
oxide  and  hydrogen  in  the  volume  ratio  of  1-2, the  following  re- 
action will  take  place 

2N0  +-  H2  H20  + N20 

and  for  2 volumes  of  nitric  oxide  and  8 volumes  of  hydrogen  the 
equation  is 

2N0  + 4H2 —NH20H  NH40H 

Sabatier  and  Senderens,-  Neogie  and  Adhicary  used  nickel  and 
copper  as  catalysers.  They  passed  a mixture  of  nitric  oxide  and 


of 


hydrogen  thru  a glass  tube  which  contained  finely  divided  nickel 
or  copper  at  temperatures  ranging  from  150-250  'C.  The  resulting 
product  was  ammonia  and  nitrogen. 

According  to  Divers  and  Hagaf  Dummreicher*  and  Chesneau,^ 
Hydroxylamine  and  ammonia  are  produced  when  nitric  oxide  is  passed 
thru  a series  of  gas-washing  bottles  containing  tin  and  cone, 
hydrochloric  acid..  The  yields,  however, are  small  and  the  separa- 
tion of  the  Hydroxylamine  hydrochloride  is  not  easily  accomplished. 

Chesneau1' experimenting  with  a solution  of  chromous  chloride 
claims  to  have  reduced  nitric  oxide  to  Hydroxylamine  and  ammonia. 

He  points  out  that  a rapid  constant  amount  of  nitric  oxide  must 
be  passed  into  an  acid  solution  to  form  Hydroxylamine, otherwise 
a slow  stream  will  cause  the  formation  of  ammonia. 

Ludwig  and  Hein,  Divers  and  Haga" published  papers  in  which 
they  state  that  Hydroxylamine  can  be  obtained  in  considerable 
amounts  if  nitric  oxide  is  passed  slowly  into  a heated  mixture 
of  tin  and  hydrochloric  acid.  They  do  not  state  the  yields  ob- 
tained by  this  method. 

Chromous  chloride  solution  according  to  Chesneau  and  Kohl- 
schutter" reduces  nitric  oxide  to  ammonia  in  neutral  solutions 
while  in  acid  solution  it  reduced  to  Hydroxylamine . The  same 
authors  also  found  that  hydroiodic  acid  reduces  nitric  oxide  to 
ammonia  and  nitrous  oxide. 

)3 

Dummreicher  reports  that  stannous  chloride  in  strongly  acid 
solution  will  reduce  nitric  oxide  to  Hydroxylamine  in  small 
amounts  and  not  readily. 


/*- 

Hans  Ziehl  attempted  to  prepare  Hydroxylamine  by  the  reduc- 


tion  of  nitric  oxide  using  a colloidal  solution  of  platinum,  which 
he  prepared  by  reducing  a sightly  alkaline  solution  of  chlor- 
platinic  acid  with  hydrazine  and  adding  a small  amount  of  gum 
arabic.  Equal  volumes  of  hydrogen  and  nitric  oxide  were  passed 
under  pressure  into  a pressure  bottle  containing  the  colloidal 
platinum.  The  bottle  is  connected  to  a shaking  devise  and  sha- 
ken vigerously.  Ziehl  found  that  no  Hydroxylamine  was  formed  by 
this  method  but  that  his  final  product  consisted  of  ammonia  and 
nitrogen.  A mixture  consisting  of  2 volumes  of  nitric  oxide  and 
3 volumes  of  hydrogen  was  tried  but  as  before  he  obtained  ammonia 
and  nitrogen.  They  found  that  82.34$  of  the  nitric  oxide  was 
changed  to  nitrogen  while  15.73$  became  ammonia. 

Divers  and  Haga'have  succeeded  in  obtaining  Hydroxylamine 
in  the  following  manner.  If  sodium  sulphide  and  sodium  nitrite 
in  solution  are  mixed, then  acidified  and  boiled, Hydroxylamine  is 
formed, and  when  the  sulphide  is  in  the  proportion  of  2 mols  to 
1 mol  of  the  nitrite, and  the  hydrochloric  acid  added  very  slowly, 
almost  all  of  the  nitrogen  is  found  on  titration  with  iodine  to 
have  been  converted  into  Hydroxylamine. 

NaN02  -r  2Na2S03  + HOH  t RHCL — ^NH20H,HC1  3Nacl  2NaHS04 

On  evaporating  the  acid  solution, separating  the  sodium  salts  by 
absolute  alcohol  and  evaporating  again, Hydroxylamine  sulphate 
separates  out.  Further  experiment  proved  that  sodium  meta- 
sulphide used  with  sodium  nitrite  gave  the  best  yield  of  Hydroxy- 
lamine sulphate. 

In  1387  Raschig  reported  that  Hydroxylamine  can  be  gotten 


from  a nitrite  by  sulphonation  followed  by  hydrolysis.  Divers 


....  it  m 'M  111.  I 

* 


3 

and  Haga  working  on  the  suggestion  given  by  Raschig's  work  used  a 
concentrated  solution  of  2 raols  of  commercial  sodium  nitrite, 1 mol 
of  sodium  carbonate  and  then  treated  the  solution  with  sulphur 
dioxide  until  just  acid, while  it  was  kept  well  agitated  at2-3'"C 
below  zero.  It  was  claimed  by  them  that  at  this  temperature  sul- 
phur dioxide  will  not  act  on  Hydroxylamine  but  will  reduce  the 

nitrite  completely.  At  this  temperature  the  conversion  of  the  ni- 

S * 2 

trite  into  oximido-sulphonate^'^v,  cr<?A<*  appears  to  be  complete. 

~ O A'<X’ 

When  gently  warmed  with  a few  drops  of  sulphuric  acid, the  oximido- 
sulphonate  rapidly  by  hydrolysis, with  mark  rise  in  temperature  into 
oxyamido-sulphonate  and  sodium  acid  sulphate.  The  solution  of  the 
salts  is  kept  at  90-95  G for  two  days,  by  the  end  of  which  time  all 
the  oxyamido-sulphonate  will  have  hydrolysed  into  Hydroxylamine 
sulphate. 

B. B.Adhikary  in  writing  on  the  reduction  of  nitric  oxide 
by  contact  action  of  metals  and  metallic  oxides  states  that  he 
passed  a mixture  of  nitric  oxide  and  hydrogen  over  gold, silver, 
magnesium, tin, antimony , bismuth  and  iron  at  various  temperatures  and 
in  all  cases  ammonia  and  water  were  the  final  products. 

Z) 

E.P.Schoch  and  R.H. Pritchett  after  trying  various  other 
methods  found  that  the  preparation  of  Hydroxylamine  by  the  electro- 
lytic reduction  of  nitric  acid  according  to  the  method  of  Julius 
Tafel,  to  produce  the  largest  yields.  The  apparatus  used  was  iden- 
tical with  that  of  Tafel fs  except  that  the  anode  is  a lead  rod  or 
pipe  about  one  inch  in  diameter;  this  was  used  in  place  of  the 
graphite  anode  employed  by  Tafel, because  they  found  it  necessary  to 
use  dilute  sulphuric  acid  in  the  anode  compartment.  The  Hydroxyla- 


mine  hydrochloride  was  freed  from  the  accompanying  ammonium  chloride 
produced, by  extraction  with  cold  absolute  alcohol.  They  claim  to 
have  obtained  about  80%  of  the  theoretical  amount  possible. 

Other  work  too  numerous  to  mention  has  been  done  upon  the 
preparation  of  Hydroxylamine , but  the  methods  are  only  of  theoretical 
importance  and  therefore  will  not  be  mentioned  here. 

III.  Purpose  of  Work. 

As  it  will  be  seen  from  the  preceding  pages, very  few  exper- 
iments have  been  performed  using  a catalyist  for  promoting  the  re- 
duction of  the  nitric  oxide  to  Hydroxylamine.  In  view  of  the  diffi- 
cult methods  used  for  recovering  Hydroxylamine  from  the  by-products 
by  the  reaction  it  was  deemed  that, if  possible , some  method  might  be 
devised  for  preparing  Hydroxylamine  by  the  use  of  two  gases, one  of 
them  to  be  nitric  oxide  and  the  other  some  reducing  gas  as  sulphur 
dioxide, hydrogen, hydrogen  sulphide, etc . , in  the  presence  of  a cat- 
alyist. In  this  manner  interfering  by-products  would  be  eliminated 
and  the  Hydroxylamine  easily  and  quickly  separated.  It  will  be  noti- 
ced from  Ziehls  and  Sabatier  and  Senderens (loc.  cit.)  work  using 
colloidal  platinum  and  nickel  respectivily , that  the  reduction  does 
not  stop  at  Hydroxylamine  but  continues  to  ammonia.  To  secure  a 
catalyist  which  would  promote  the  reduction  of  nitric  oxide  to 
Hydroxylamine  and  stop  there, seemed  to  be  the  key  to  the  solution  of 
this  problem, so  it  was  thus  made  the  object  of  this  paper.  It  was 


' 


PH 

^ | ijg§ 


thot  advisable  to  undertake  various  methods  of  reduction  and  deter- 


mine the  effect  different  catalyist  had  on  the  reaction.  Once  the 
reduction  of  nitric  oxide  to  Hydroxylamine  was  accomplished, a 
method  02  separation  and  purification  would  be  a comparatively  sim- 
ple task  because  of  the  absence  of  interfering  substances. 

Altho  Schoch  and  Pritchett  (loc.cit.)  xhave  obtained 
Hydroxylamine  by  the  electrolytic  reduction  of  nitric  acid  and 
claim  to  have  obtained  as  much  as  80%  of  the  theoretical  yield, we 
did  not  attempt  to  obtain  Hydroxylamine  by  an  electrical  method  but 
have  confined  ourselves  to  its  production  by  strictly  chemical 
means. 

The  method  to  be  used  for  the  detection  Hydroxylamine  was 
the  reduction  of  Fehling's  solution.  Very  minute  amounts  of 
Hydroxylamine  of  its  salts  are  sufficient  to  cause  the  formation 
of  the  brown  copper  oxide. 

IV.  Experimental . 

According  to  Sabatier  and  Sendereiis  (loc.cit.)  the  activity 
of  nickel  as  a catalyist  is  nil  at  low  temperatures, but  at  250-300' 0 
nickel  is  quite  active.  It  was  decided  to  see  if  nickel  at  a tem- 
perature of  100-115°C  would  catalyse  the  reduction  of  nitric  oxide 
to  Hydroxylamine, and  not  to  ammonia.  The  apparatus  used  is  shown 
on  Figure  1 . 

Preparation  of  Catalyserr-The  catalyser  was  made  by  melting 

nickel  nitrate  in  its  own  water  of  crystalization  in  a nickel  cruci- 


ole  and  then  inpregnat ing  animal  charcoal  with  the  solution.  The 
inpregnated  charcoal  was  then  heated  in  the  crucible  to  form  the 
nickel  oxide.  It  was  placed  in  a glass  conbustion  tube  heated  to 

c 

^50-300  C,and  reduced  with  a stream  of  hydrogen  for  three  hours. 

Procedure  — 3he  tube, after  the  reduction  of  the  nickel 
oxide  had  taken  place, was  allowed  to  cool  slowly  to  105  G with 
hydrogen  still  passing  thru.  A mixture  of  2 volumes  of  hydrogen 
and  one  volume  of  nitric  oxide  was  slowly  passed  thru  the  tube, the 
temperature  being  maintained  about  110  C,the  alkaline  gases  pro- 
duced were  absorbed  in  dilute  hydrochloric  acid.  When  the  run  was 
completed  this  acid  solution  was  examined  for  Hydroxylamine  by 
adding  a little  of  the  solution  to  Fehling's  solutions.  No  reduc- 
tion of  the  Fehling's  solution  occured  which  proved  the  absence  of 
Hydroxylamine.  On  opening  the  tube  it  was  found  to  smell  very 
strongly  of  ammonia.  The  hydrochloric  acid  solution  was  evaporated 
lo  dryness  on  a water  bath, the  residue  broken  up  and  again  tested 
for  Hydroxylamine  and  ammonia.  No  Hydroxylamine  hydrochloride  was 
found  to  be  present  but  on  heating  a little  of  the  residue  with  so- 
dium hydroxide , the  odor  of  ammonia  was  easily  detected.  Another 
run  was  made  using  equal  volumes  of  nitric  oxide  and  hydrogen  but 
as  before  ammonia  was  the  final  product. 

A statement  is  found  in  many  text  books  that  Hydroxylamine 


can  be  prepared  by  passing  nitric  oxide  thru  a solution  of  tin- 
dissolving  in  hydrochloric  acid.  No  mention,however , is  made  in 
regards  to  the  amounts  obtained  and  so  in  order  to  get  some  idea 


of  the  yield  of  Hydroxylamine  produced, by  this  method, it  was  deci- 
ded to  repeat  the  procedure  using  metallic  mercury  as  a catalyser. 

Procedure- -The  apparatus  is  shown  in  Figure  2.  In  each  of 
the  gas  washing  bottles  was  placed  tinfoil  cut  into  very  small 
squares,  and  covered  with  a dilute  solution  of  hydrochloric  acid. 

The  two  gases  nitric  oxide  and  hydrogen  in  equal  volumes  were 
bubbled  thru  the  bottles  at  a uniform  rate  of  approximately  30 
bubbles  per  minute.  The  tin  in  dissolving  gives  up  nascent  hydro- 
gen according  to  the  equation 

Sn  2H01  = SnC12  + H2 

which  was  expected  to  x-educe  the  nitric  oxide  while  stannous  chlor- 
ide ana  mercury  might  catalyse  the  reduction.  After  fourteen  liters 
of  each  gas  had  been  passed  thru  the  bottles, the  solutions  from 
each  of  the  bottles  were  combined  in  a large  Erlenmeyer  flask, water 
added  and  the  tin  precipitated  out  with  hydrogen  sulphide.  Two  pre- 
cipitations were  necessary  to  separate  alx  of  uhe  tin.  T**e  solution 
was  then  filtered,  washed  and  the  filtrate  evaporated  to  dryness  on 

a water  bath,  ihe  residue  was  examined  for  Hydroxylamine  but  no 
reduction  of  Fehling’s  solution  occured.  It  was  then  tested  for 

ammonia  which  was  found  to  be  present,  mercury  being  omitted  anot- 
her run  similar  to  the  first  gave  ammonia  as  the  only  product. 

It  was  apparent  from  the  preceding  experiments  that  if 
satisfactory  yields  are  to  be  obtained  a more  intimate  and  longer 
contact  should  be  made  between  the  gases  and  the  catalyser*  With 
this  idea  in  mind  an  apparatus  as  shown  in  Figure  3, was  constructed. 


Apparatus- -This  consisted  of  an  tight  cast  iron  cylinder 
about  .3  feet  tall  and  8M  in  diameter.  The  valve  at  the  top  was  used 
to  regulate  the  flow  of  the  gases  while  the  one  at  the  bottom  was 
connected  with  the  water  main  by  means  of  which,  water  could  be  for- 
ced in  compressing  the  gases  to  o.ny  required  pressure  up  to  40#. 

By  means  of  a hollow  copper  „ube  bent  in  spiral  shape  the  gases 
could  be  connected  to  a pressure  bottlewhich  was  mounted  on  a 
shaking  devise.  Nitric  oxide  was  prepared  by  mixing  in  a flask, 

200  grams  of  ferrous  sulphate  with  40  grams  of  potassium  nitrate 
and  dropping  hot  dilute  sulphuric  acid  on  the  mixture, the  gas  evol- 
ved being  collected  in  gasometers.  The  gas  cylinder  was  filled 
with  water, the  hollow  copper  tube  connected  with  the  gasometer  and 
the  gas  forced  in  under  a water  head  contained  in  a connecting 
gasometer.  The  valve  at  the  bottom  of  the  cylinder  being  opened 

simultaneously  with  the  valve  at  the  top.  After  twelve  liters  of 
nitric  oxide  had  been  forced  in  both  valves  were  closed  and  connec- 
tion made  with  a hydrogen  tank.  The  upper  valve  was  then  opened 
and  hydrogen  forced  in  until  the  gauge  on  the  cylinder  showed  25# 
pressure, after  which  the  valve  was  closed.  In  the  pressure  bottle 
was  placed  a colloidal  solution  of  platinum  prepared  according  to 

directions  given  by  H.L.Lockte  of  the  University  of  Illinois. 

Preparation  of  Gatal.yist--About  .3  gram  of  platinum  was 
dissolved  in  aqua  regia  and  evaporated  to  dryness  twice, then  taken 
up  with  hydrochloric  acid.  The  chlor-platinic  acid  thus  formed 
was  poured  into  a beaker  containing  250  c.c.of  water  made  slightly 
alkaline  with  sodium  hydroxide. 


Approximately  .3  gram  of  gum  arable  in  water  solution  was  added, 
and  a few  crystals  of  hydrazine  hydrochloride  were  dropped  into  the 
solution.  Reduction  took  place  almost  immediately  after  which  the 
solution  was  made  acidic  with  hydrochloric  acid.  The  solution  was 
poured  into  the  pressure  bottle, the  bottle  evacuated  and  connection 
made  to  the  gas  cylinder. 

Procedure- -The  motor  was  started  and  the  solution 
shaken  for  six  hours  during  which  time  the  reading  on  the  gauge 
was  carefully  noted.  No  decrease  on  the  gauge  reading  was  observed 
during  the  run.  The  bottle  was  then  disconnected  and  the  solution 
poured  into  a flask  containing  a volume  of  acetone  equal  to  that 
of  the  solution.  This  acetone  solution  wa3  allowed  to  stand  over 
night  and  then  filtered  to  remove  the  precipitated  platinum.  The 
filtrate  was  then  tested  for  Hydroxylamine  with  Fehling'3  solution, 
but  no  reduction  was  observed.  On  evaporating  the  solution  to  dry- 
ness no  residue  was  left  proving  that  nitric  oxide  and  hydrogen  in 
the  presence  of  colloidal  platinum  would  not  react. 

Platinum  as  the  Catalyist--A  active  form  of  platinum  has 
been  developed  in  the  organic  division  of  the  University  of  Illinois, 
which  has  been  very  successful  in  reducing  many  organic  compounds. 

It  was  thot  that  it  might  also  promote  the  reduction  of  nitric  oxide. 


Preparation  of  the  data! yiist- -About  .4-. 5 gram  of  platinic 
chloride  was  dissolved  in  a mixture  of  5 grams  of  sodium  nitrate 


. 


. 


. 


. 


I 1$ 

- 


and  4 grams  of  potassium  nitrate  and  the  mixture  evapotated  to  dry- 
ness on  a water  bath.  It  was  then  fused  to  a quiet  liquid  and 
allowed  to  cool, after  which  it  was  dissolved  in  water  and  filtered. 
The  platinum  precipitate  on  the  filter  paper  was  washed  with  water 
until  free  from  salts.  It  was  then  washed  into  the  pressure  bottle 
and  the  filter  paper  saved  to  be  used  again  to  filter  off  the  plat- 
inum after  the  run  was  completed. 

Procedure- -The  solution  in  the  pressure  bottle  was  made 
acid  with  hydrochloric  acid, the  bottle  evacuated  and  connections 
made.  The  bottle  was  shaken  for  six  hours, the  solution  removed, 
filtered  and  evaporated  to  dryness.  No  residue  was  left  showing 
that  the  platinum  used  as  a catalyser  did  not  have  any  effect  in 
aiding  hydrogen  reduce  nitric  oxide. 

Mercury  as  the  Catalvist- -Using  the  same  pressure  appar- 
atus as  previously  described, 15  grams  of  mercurous  chloride  and 
20  grams  of  stannous  chloride  were  placed  in  the  pressure  bottle 
and  200  c.c.  of  water  containing  15c. c.  of  dilute  hydrochloric 
acid  were  added.  The  bottle  was  evacuated  and  connections  made 
with  the  gas  cylinder.  The  bottle  was  shaken  for  six  hours  and  the 
gauge  reading  carefully  observed.  The  mercurous  chloride  was  re- 
duced to  black  metallic  mercury  by  the  stannous  chloride.  It  was 
thot  that  the  stannous  chloride  in  conjunction  with  the  hydrogen 
formed  by  the  reaction  would  act  as  a reducing  agent  in  the  pre- 
«ence  of  metallic  mercury  as  the  catalyist.  The  gauge  reading 
showed  no  decrease  after  the  six  hours.  The  solution  was  removed 
from  the  flask,  almost  neutralized  by  sodium  hydroxide  and  the  tin 


precipitated  out  by  hydrogen  sulphide.  A small  amount  of  the  mer- 
cury was  also  precipitated  by  the  hydrogen  sulphide  but  the  major 
amount  was  removed  when  the  solution  was  filtered.  The  solution 
was  then  evaporated  to  dryness  on  a water  bath  and  the  residue  tested 
for  Hydroxylamine.  The  residue  was  composed  completely  of  sodium 
chloride, no  Hydroxylamine  or  ammonia  being  formed. 

Reduction  by  Chromous  Chloride--Chesneau  and  Kohls chutter 
(loc.cit.)in  their  paper  on  the  reduction  of  nitric  oxide  by  means 
of  chromous  chloride  found  that  when  nitric  oxide  was  passed  into 
a neutral  solution  of  chromous  chloride  that  ammonia  would  be  the 
final  product  while  in  an  acid  solution  Hydroxylamine  would  be 
formed.  They  state,  however, that  nitric  oxide  must  be  passed  into 
the  acid  solution  of  chromous  chloride  in  order  to  secure  Hydroxyl- 
amine, otherwise  ammonia  would  be  formed.  A run  was  therefore  made 
using  chromous  chloride  in  ian  acid  solution  as  a reducing  agent. 

Preparation  of  the  Chromous  Chloride- -Metallic  chronium 
was  ground  up  to  a fine  powder  and  100  c.c.  of  water  and  50  c.c.  of 
hydrochloric  acid  added.  The  mixture  was  then  poured  quickly  into 
the  pressure  bottle  which  was  then  evacuated  and  connections  made 
with  the  gas  tank. 

Procedure- -The  bottle  was  shaken  for  ten  hours  after  which 
time  the  solution  was  removed, filtered  and  made  alkaline  with  sodium 
hydroxide  which  precipitated  all  of  the  chronium.  This  was  filtered 
off  and  the  solution  tested  for  Hydroxylamine.  No  reduction  of  the 
Fehling's  solution  took  place.  ihe  solution  was  evaporated  slightly, 


then  made  acidic,  evaporated  to  dryness, and  again  tested  for  Hydro x- 
ylamine.  After  a negative  result  had  been  obtained  it  was  tested 

for  ammonia  which  was  found  to  be  present  in  considerable  amounts. 

It  is  evident  that  the  chroinous  chloride  caused  the  reduction  to 
procede  to  ammonia  and  not  to  Hydroxylamine.  It  was  thot, however, 
in  view  of  Chesneau  and  Kohl s chut ter ' s work  that  some  Hydroxylamine 
should  have  been  formed.  In  order  to  ascertain  if  the  above  authors 
really  secured  Hydroxylamine  as  they  claim, their  work  was  repeated. 
The  apparatus  used  is  shown  in  Figure  4.  Nitric  oxide  from  a gas- 
ometer was  passed  rapidly  into  an  acid  solution  of  chromous  chloride 
protected  from  air  by  a layer  of  petroleum  ether.  The  residual  gas 
was  collected  in  another  gasometer  and  again  passed  thru  the  chrora- 
ous  chloride  solution.  This  procedure  was  repeated  several  times, 
until  a marked  decrease  in  the  volume  of  nitric  oxide  was  observed. 
The  solution  was  poured  into  a separatory  funnel  and  the  chroinous 
chloride  solution  drawn  off.  It  was  then  made  alkaline  with  sodium 
hydroxide  and  the  precipitated  chromium  filtered  off.  The  filtrate 
was  evaporated  to  dryness  and  the  residue  tested  for  Hydroxylamine. 

No  reduction  of  the  Fehling's  solution  took  place.  It  was  then 
examined  for  ammonia  \vhich  was  again  found  to  be  present  in  consider- 
able amounts. 

The  experiment  was  again  repeated, all  possible  care  in 
following  directions  was  taken, samples  of  the  chromous  chloride 
solution  being  tested  every  few  minutes, but  at  no  time  could  any 
positive  test  for  Hydroxylamine  be  obtained.  Altho  Chesneau  and 
Kohlschutter  claim  to  have  obtained  Hydroxylamine  in  this  manner. 


' 


. 

. 


we  do  not  believe  it  possible  that  Hydroxylamine  could  be  formed 
and  stay  in  the  solution  as  Hydroxylamine  in  the  presence  of  such 
a powerful  reducing  agent  as  chromous  chloride.  It  may  be  possible 
that  Hydroxylamine  is  formed  as  an  intermediate  product, but  our 
belief  is  that  it  is  immediately  reduced  to  ammonia. 

Nickel  as  the  Catalyser- -In  view  of  previous  research  and 
our  own  results, it  was  decided  that  the  platinum  group  could  not  be 
used  as  catalysers  due  to  the  fact  that  Hydroxylamine  will  decompose 
in  the  presence  of  colloidal  platinum  and  platinum  black.  In  a paper 
published  by  A. Findlay  and  W. Thomas  the  products  of  the  decomposi- 
tion are  said  to  be  ammonia  nitrogen  and  nitrous  oxide.  B.Adhikary 
(loc.cit.)  did  all  his  work  at  temperatures  over  100  G.  A search  of 
the  literature  failed  to  reveal  any  statements  regarding  the  use  of 
lower  temperatures.  If  at  over  100° C nickel  changes  nitric  oxide 
to  ammonia, would  it  not  be  possible  at  temperatures  up  to  90  G that 
the  reducing  action  would  not  be  so  strong  and  instead  of  reducing 
the  nitric  oxide  to  ammonia  it  might  stop  at  Hydroxylamine? 

Preparation  and  Use  of  the  Gatalyist--A  nickel  catalyser 
which  had  been  prepared  Dy  reducing  nickel  nitrate, was  put  into  the 
pressure  bottle, water  added, the  bottle  evacuated  and  connected  to 
the  gas  cylinder.  After  opening  up  the  cylinder  valve, the  bottle 
was  shaken  for  three  hours  at  ordinary  temperature.  No  decrease 
could  be  observed  in  the  gauge  reading.  The  temperature  of  the 
solution  was  raised  gradually  by  placing  a small  flame  under  the 
bottle  and  surrounding  the  shaking  bottle  by  an  asbestos  box  to 
keep  the  heat  in.  A temperature  of  about  80-90  C could  be  obtained 
in  this  manner. 


The  bottle  was  shaken  for  three  more  hours, the  flame  remo- 
ved and  the  bottle  with  solution  allowed  to  c^ol  while  shaking. 

The  solution  was  filtered  to  remove  the  nickel,  and  a small  amount 
of  hydrochloric  acid  added  to  the  filtrate.  The  latter  was  evapor- 
ated to  dryness  but  no  residue  was  left  showing  that  at  tempera- 
tures below  100  G nickel  did  not  catalyse  the  reduction  of  nitric 
oxide  in  a water  solution. 

Reduction  by  Means  of  ned  Phosphorus- -Among  the  chemical 
properties  of  red  phosphorus  is  listed  the  fact  that  concentrated 
nitric  acid  is  reduced  with  almost  explosive  violence  while  dilute 
nitric  acid  evolves  nitrous  fumes  in  the  presence  of  red  phosphor- 
us. Because  of  the  reducing  action  it  appeared  possible  that  the 
red  phosphorus  might  also  reduce  nitric  oxide.  A mixture  of  the 
red  phosphorus  and  water  was  put  into  the  reactian  bottle  and  nit- 
ric acid  bubbled  thru  the  solution.  In  conjunction  with  this 
method, red  phosphorus  and  water  were  also  put  in  the  pressure  bott- 
le, connection  made  with  the  gas  cylinder  and  the  bottle  shaken  for 
three  hours.  The  nitric  oxide  in  the  gasometer  was  passed  back  and 
forth  several  times  thru  the  reaction  bottle.  The  solutions  were 
taken  from  the  reaction  and  pressure  bottles, filtered  and  evapora- 
ted to  dryness  after  10  c.c.  of  hydrochloric  acid  had  been  added. 

) 

No  residue  is  left  proving  red  phosphorus  would  not  cause  the  re- 
duction of  nitric  oxide.  In  another  run  potassium  iodide  was  add- 
ed as  a catalyser,but  the  result  was  similar  to  the  first  as  no 
Hydroxylaraine  was  obtained. 


The  Use  of  Sodium  Amalgam  as  the  Reducing  Agent- -The  reduc- 
tion of  many  organic  compounds  by  sodium  amalgam  led  to  the  belief 
that  it  might  aid  in  the  reduction  of  nitric  oxide.  An  amalgam 
containing  .214$  sodium  was  put  into  the  pressure  bottle,  connec- 
tions made  and  the  bottle  shaken  for  eight  hours.  It  was  removed 
from  the  bottle,  filtered  to  remove  the  amalgam, a small  amount  of' 
hydrochloric  acid  added  and  the  solution  evaporated  to  dryness. 

No  residue  was  obtained. 

Catalytic  Reduction  by  Means  of  Palladium  Asbestos 

Sabatier  and  Senderens  have  shown  that  in  the  presence  of  palla- 
dium sponge  previously  saturated  with  hydrogen, nitric  oxide  is  com- 
pletely converted  into  water  and  ammonia.  Their  work  was  repeated 
by  us  with  the  exception  that  instead  of  palladium  sponge  being 
used  we  worked  with  palladium  asbestos.  The  two  gases, nitric  oxide 
and  hydrogen  were  preheated  before  passing  over  the  catalyist. 

A diagram  of  the  apparatus  is  shown  in  Figure  5.  Nitric  oxide  and 
hydrogen  were  passed  thru  gas-washing  bottles  containing  sulphuric 
acid  and  then  thru  a short  piece  of  heavy  glass  tubing  about  three- 
fourths  of  an  inoh  in  diameter, where  they  were  heated  slightly.  The 
preheated  gases  were  then  passed  thru  the  catalyser  tube  containing 
the  palladium  into  a dilute  solution  of  hydrochloric  acid.  On  exam- 
ination of  the  hydrochloric  acid  solution  it  was  found  to  contain 
ammonium  chloride  only, no  Hydroxylaraine  being  formed. 


Reduction  by  Use  of  Sulphur  Dioxide-- In  Divers  and  Haga 
(loc.cit.)  publication, state  that  they  have  obtained  Hydroxy lamine 
using  sodium  nitrite  and  sodium  sulphite  according  to  the  equation. 

NaN02  + 2Na2S03  + HOH  +■  4HC1  = NH20H  HG1  3NaCl  -f  2NaHS04 
It  would  seem  from  the  above  equation  that  sulphur  dioxide  is  the 

Z3 

active  reducing  agent.  Tanatar, however , claims  that  sulphur  dioxide 
will  attack  Hydroxylamine  reducing  it  to  ammonium  sulphate.  Divers 
and  Haga's  method  was  repeated  by  us, all  directions  being  carefully 
followed.  Sodium  nitrite  and  sodium  sulphite  were  mixed  in  the  pro- 
portions as  given  by  the  equation, water  added  and  the  hydrochloric 
acid  added  very  slowly.  The  solution  was  evaporated  to  dryness, an 
absolute  alcbhol  extraction  made  but  no  Hydro xyiamine  was  found  to 
be  present.  The  method  was  again  repeated  but  as  before  no  test  for 
Hydroxylamine  could  be  obtained.  It  was  noticed  that  on  each  addi- 
tion of  the  hydrochloric  acid  a sharp  rise  in  temperature  followed. 

To  determine  if  this  rise  in  temperature  was  the  cause  of  the  non- 
formation of  Hydroxylamine, the  flask  was  placed  in  an  ice-salt  bath 
about  -10JC.  The  hydrochloric  acid  was  added  very  slowly  to  the 
solutions  of  the  salts  and  at  no  time  was  the  temperature  above  -5  G 
The  solution  was  then  placed  in  evaporating  dishes  and  evap- 
orated  to  dryness.  B efore  evaporation  the  solution  was  boiled  for 
an  hour  to  expell  as  much  as  possible  of  the  sulphur  dioxide.  On 
testing  the  residue, Hydroxylamine  was  found  to  be  present,  It  was 
extracted  with  absolute  alcohol  and  the  alcohol  distilled  oil, leaving 
a small  amount  of  Hydroxylamine  sulphate  as  a residue.  The  separa- 
tion of  Hydroxylamine  sulphate  from  the  by-products, sodium  chloride 


- 


and  sodium  acid  sulphate  is  not  complete  because  of  the  tendency 

of  these  salts  to  occlude  small  amounts  of  Hydroxylamine  sulphate. 
Several  extractions  are  necessary  to  completely  remove  all  the 
Hydroxylamine  sulphate.  It  is  important  to  note  that  unless  the 
reaction  is  carried  out  at  low  temperatures  and  the  hydrochloric 
acid  added  very  slowly, no  Hydroxylamine  sulphate  will  be  formed. 

A possible  explanation  for  this  fact  is  that  at  room  temperatures, 
sulphur  dioxide  will  attack  the  Hydroxylamine  formed  and  convert  it 
into  ammonium  sulphate, while  at  temperatures  below  G^C,  sulphur 
dioxide  will  complete  the  reduction  but  will  not  act  on  the  Hydrox- 
y 1 am in e formed. 

Since  Hydroxylamine  can  be  formed  by  the  reduction  of  a 
nitrite, would  it  not  be  possible  that  nitric  oxide  could  be  reduced 
in  a similar  manner?  Qn  account  of  the  very  slight  solubility  of 
nitric  oxide  in  water , advantage  was  taken  of  the  fact  that  nitric 
oxide  will  form  an  addition  compound  with  ferrous  sulphate  in 
Water  solution.  An  apparatus  such  as  shown  in  Figure  6,  served  the 
purpose  very  well.  About  8-10  grams  of  ferrous  sulphate  was  dis- 
solved in  600  c.c.  of  water  and  the  solution ' poured  into  a large 
wide-mouthed  bottle.  Nitric  oxide  made  from  ferrous  sulphate, 
potassium  nitrate  and  dilute  sulphuric  acid  was  passed  into  the 
water  solution  until  it  became  a dark  brown  color.  Sulphur  dio- 
xide made  by  dropping  sulphuric  acid  on  sodium  bisulphate  was  also 
passed  into  the  water  solution.  The  bottle  was  then  immersed  in 
an  ice-salt  bath  and  the  solution  stirred  vigorously  with  a glass 
stirrer. 


' 


. 

• 

. 

•• 

1 

ure 


Approximately  10  liters  of  nitric  oxide  and  15  liters  of 
sulphur  dioxide  were  passed  into  the  solution.  After  shaking  for 
an  hour  the  solution  turned  to  a white  color.  It  was  then  removed, 
allowed  to  come  to  room  temperature.  A small  amount  of  the  sol- 
ution was  tested  with  barium  chloride, which  gave  a white  precipi- 
tate showing  that  the  sulphur  dioxide  had  been  oxidized  to  sulphu- 
ric acid»  Sodium  hydroxide  was  added  to  precipitate  all  the  iron 
and  the  solution  filtered.  The  filtrate  was  made  acidic  with 
sulphuric  acid  and  evaporated  to  dryness.  No  test  for  Hydroxyl- 
amine  was  obtained. 

In  all  probability  Hydroxy lamine  was  immediately  reduced  by 
the  ferrous  sulphate  or  by  the  sulphur  dioxide.  According  to 
Tanar  (loc.cit.)  when  a solution  of  Hydroxylamine  sulphate  is 
saturated  with  sulphur  dioxide, kept  over  night  and  evaporated  to 
dryness  on  a water  bath, ammonium  sulphate  is  formed. 

Reaction  with  Hydraztne--To  ascertain  whether  hydrazine 

would  reduce  nitric  oxide, about  10  grams  of  it  in  water  solution 

flv  vol*' 

was  put  into  a bottle  and  nitric  bubbled  thru.  Examination  of 
the  solution  proved  that  no  reduction  had  taken  place. 


V.  Discussion. 

It  will  be  seen  from  our  results  that  the  preparation  of 
Hydroxylamine  by  a strictly  chemical  method  is  difficult  and, in 
many  cases, without  success, the  direct  cause  of  the  failure  to  pro- 
duce Hydroxylamine  by  some  of  the  methods  tried  was  due  mainly  to 
the  great  susceptibility  of  Hydroxylamine  to  the  action  of  many 
substances  which  either  decompose  it  as  quickly  as  it  is  formed  or 
reduces  it  at  once  to  ammonia. 

It  should  be  noted  that  low  temperatures  are  conducive  to 
the  production  of . Hydroxylamine, higher  temperatures  causing  the 
formation  of  ammonia, nitrogen  and  nitrous  oxide.  This  fact  pro- 
hibits the  use  of  such  catalyists  as  nickel, copper , iron, etc . , 
which  require  temperatures  over  100  G before  they  become  active 
and  thus  our  work  was  confined  to  the  use  of  the  platinum  group. 

It  was  shown  that  nickel  in  a x&ter*  solution  at  8 Q-9G  G does  not 
cause  the  reduction  of  nitric  oxide.  The  action  of  the  catalyist 
used  in  this  research  either  caused  the  decomposition  or  reduction 
of  the  Hydroxylamine  formed  or  else  had  no  effect  on  the  reaction. 
No  catalyser  has  been  found  which  would  promote  the  reduction  to 
Hydroxylamine  and  not  to  ammonia. 

Hydroxylamine  sulphate  was  obtained  us  using  Diver's  and 
Haga's  (loc.cit.)  method, but  the  amount  obtained  was  small  and  a 
complete  extraction  difficult.  The  attempt  to  reduce  nitric  oxide 
by  sulphur  dioxide  in  the  presence  of  ferrous  sulphate  as  might 
have  been  expected  because  of  the  action  of  both  ferrous  sulphate 
and  sulphur  dioxide  in  decomposing  any  Hydroxylamine  formed. 


If  it  were  possible  to  procure  some  substance,  the  addition  of  which, 
would  cause  the  Hydroxylamine  to  be  precipitated  as  soon  as  it  were 
formed, the  solution  of  this  problem  might  be  solved. 

VI.  Summary . 

I.  Nitric  oxide  will  not  be  reduced  in  the  presence  of 
colloidal  or  finely  divided  platinum  used  as  a catalyist. 

II.  At  temperatures  below  100-C  nickel  is  not  active 
while  at  higher  temperatures  it  will  promote  the  reduction  of 
nitric  oxide  to  ammonia. 

III.  Strong  reducing  agents  such  as  chromous  chloride 
reduce  nitric  oxide  to  ammonia, no  Hydroxylamine  being  formed. 

IV.  Salts  of  Hydroxylamine  in  a saturated  solution  of 
sulphur  dioxide  and  in  the  presence  of  ferrous  sulphate  are  reduced 
to  ammonia, if  allowed  to  stand  at  room  temperature  for  several 
hours . 

V.  Substances  such  as  metallic  mercury, red  phosphorus, 
sodium  amalgam, stannous  chloride, and  hydrazine  do  not  cause  the 
reduction  of  nitric  oxide  to  proceed  to  the  formation  of  Hydroxyl- 
amine . 


■ 


■ 


. 

■ 


VII.  Bibliography . 


1.  Faraday:  Pogg.  Ann.  33-149  (1834). 

2.  F.Kuhlmann:  A.  29,286,  (1839). 

3.  Jouve:  Comp. rend.  128,435,  (1899). 

4.  Cooke:  C.1327,  (1888). 

5.  Sabatier  and  Senderen3:  Comp. rend.  135,278,  (1902). 

3.  Neogie  and  Adhicary:  C.  463,  (l$ll). 

Divers  and  Haga:  J.Chem.Soc.  47,623,  (1899). 

8.  Dummreicher : W.Ak.B.  82,560,  (1880). 

9.  Chesneau:  C.R.  129,100,  (1899). 

10.  Ludwig  and  Hein:  B.2,671,  (i860), 

11.  Divers  and  Haga:  J.Chem.Soc.  47,623.  (1885). 

12.  Chesneau  and  Kohlschutter : B.  37,3093,(1904). 

13.  Dummreicher:  Abstract  J.Chem.Soc.  331,  (1882). 

14.  H.Ziehl:  Doctor’s  Thesis  "Katalytische  Hydrierung  von  Stick- 

stof fverbindungen,  G-ottingen.  (1914). 

15.  Divers  and  Haga:  J.CHEM.SOC.  vol.LI.  660,(1837).  Trans. 

16.  Divers  and  Haga:  J.CHEM.SOC.  vol.59,1665,  (1896)  Trans  .II. 

17.  Raschig:  Chem.Zeit.  12,219.  (1887). 

18.  Divers  and  Haga:  J.CHEM.SOC.  Trans.  1565,  (1896). 

20.  B.B.Adhikary : Chem.News,  112,  133-4  (1915). 

21.  Schoch  and  Pritchett : J .Am. Chem. Soc . 2042-4,  (1916). 

22.  J.Tafel*.  Z. Anorg. Chem.  31,  ( 1902).  289,  ( 1902). 

23.  Tanatar: 


B.  32,241-4 


(1399) . 


